KR20160083033A - Alkoxylates of s-vinylthioalkanols - Google Patents

Abstract

(식 중,
R¹, R², R³ 은 동일 또는 상이하고, 각각 독립적으로 H, CH₃ 이며,
R⁴ 는 선형 또는 분지형 C₁-C₃₀-알킬렌이고,
R⁵, R⁶ 은 동일 또는 상이하며, 각각 독립적으로, H, C₁-C₂₀-알킬, C₃-C₁₅-시클로알킬, 아릴, -CH₂-O-C₁-C₂₀-알킬, CH₂-O-C₂-C₂₀-알케닐이고, R⁵ 및 R⁶ 은 함께 C₃-C₆-알킬렌을 형성할 수 있으며,
R⁷ 은 동일 또는 상이하고, 독립적으로, H, C₁-C₄-알킬,

이며,
R⁸ 은 C₁-C₂₂-알킬, C₂-C₂₂-알케닐이고,
n 은 2 내지 200 의 정수이다).
화학식 (I) 의 화합물을 포함하는 혼합물 및 중합체. 화학식 (I) 의 불포화 화합물을 포함하는 단량체의 자유 라디칼 중합을 수행하는 중합체의 제조 방법. 중합체-유사 반응을 포함하는 중합체의 제조 방법. 시멘트 첨가제, 시멘트 제조에서의 분쇄 보조제, 수경성 결합제에 대한 첨가제, 콘크리트 가소제, 플라스틱, 고무 또는 라텍스의 제조를 위한 반응성 가소제, 회합성 증점제 및 산화방지제로서의, 또는 폴리에테르 실록산을 제조하기 위한 화합물 (I) 을 포함하는 중합체의 용도. 이러한 중합체를 포함하는 혼합물.The unsaturated compounds of formula (I)

(Wherein,
R ¹ , R ² and R ³ are the same or different and each independently H, CH ₃ ,
R ⁴ is a linear or branched C ₁ -C ₃₀ - alkylene,
R ⁵ and R ⁶ are the same or different and are each independently selected from H, C ₁ -C ₂₀ -alkyl, C ₃ -C ₁₅ -cycloalkyl, aryl, -CH ₂ -OC ₁ -C ₂₀ -alkyl, CH ₂ -OC ₂ -C ₂₀ -alkenyl, R ⁵ and R ⁶ together may form C ₃ -C ₆ -alkylene,
R ⁷ are the same or different and, independently, H, C ₁ -C ₄ - alkyl,

Lt;
R ⁸ is C ₁ -C ₂₂ -alkyl, C ₂ -C ₂₂ -alkenyl,
and n is an integer of 2 to 200).
Mixtures and polymers comprising compounds of formula (I). A process for the preparation of a polymer which carries out the free radical polymerization of monomers comprising an unsaturated compound of formula (I). A process for preparing a polymer comprising a polymer-like reaction. As a reactive plasticizer, associative thickener and antioxidant for the production of cement additives, crushing aids in the manufacture of cements, additives for hydraulic binders, concrete plasticizers, plastics, rubbers or latexes, or for the production of polyether siloxanes ). ≪ / RTI > A mixture comprising such a polymer.

Description

BACKGROUND ART Alkoxylates of S-vinylthioalkanol {ALKOXYLATES OF S-VINYLTHIOALKANOLS}

The present invention relates to a polymer comprising an alkoxylate of an S-vinylthioalkanol and an alkoxylate of such an S-vinylthioalkanol as monomers. The present invention also provides a process for producing a polymer comprising an alkoxylate of an S-vinylthioalkanol as a monomer. The present invention also relates to such polymers and the use of mixtures comprising such polymers.

Other implementations of the invention can be deduced from the claims, the detailed description and the examples. It is to be understood that the features of the gist of the present invention described above and below can be used in different combinations as well as in specified combinations in each case without departing from the scope of the present invention. Preferred and highly preferred are, in particular, also embodiments of the invention in which all the features of the subject matter of the present invention each have a preferred and highly preferred definition.

WO 93/06142 A1 relates to the addition products of copolymers of hydroxyalkyl vinyl ethers, i.e. C2- to C4-alkylene oxides of hydroxyalkyl vinyl ethers and / or polytetrahydrofuran vinyl ethers and optionally other copolymerizable monomers .

WO 94/04580 A1 describes copolymers prepared by polymerization of water-soluble, ethylenically unsaturated monomers containing acidic groups and monomers comprising polyalkoxy sequences. The copolymer may comprise another monomer.

WO 02/066528 A2 describes alkoxylated acrylate and methacrylate macromonomers which can be used as additives in concrete. Further, WO 02/066528 A2 mentions copolymers of such macromonomers with other monomers such as acrylic acid, methacrylic acid or maleic acid.

WO 2005/000922 A1 describes dispersants for cement compositions which comprise, in particular, alkoxylated allyl alcohol sulfates and optionally other alkoxylated allyl alcohol groups as monomers.

WO 2005/005500 A1 relates to a water-soluble or water-dispersible polymer comprising an alkoxylated diallylamine derivative, an ethylenically unsaturated mono- or dicarboxylic acid, an anhydride or mixture thereof and optionally one or more further ethylenically unsaturated monomers will be. These polymers are used particularly as additives in mineral building materials.

WO 2009/040042 A1 describes polycarboxylate ethers suitable for use as concrete plasticizers or dispersants for inorganic pigments.

DE 20 58 120 describes 2-hydroxyethylvinyl sulfide, or derivatives thereof, including cationic polymers prepared by a two step process. In the first step, 2-hydroxyethyl vinyl sulfide is optionally polymerized with a comonomer such as acrylate. In the second step, the resulting (co) polymer is reacted with an alkylating agent, wherein the sulfur atom is alkylated to form a sulfonium group. The alkylating agent used may be an alkyl sulphate, such as dimethyl sulphate, an alkyl halide or an alkylene oxide, and if an alkylene oxide is used, an inorganic or organic acid should be used in the same molar amount.

Several problems arise in the production of polymers in the prior art. For example, allyl alcohol ethoxylate does not exhibit particularly high reactivity during polymerization or copolymerization, and also causes some side reactions. Isoprenol ethoxylate is also not very reactive, which can lead to the formation of isoprene in the manufacturing process. Some of the alkoxylates, such as hydroxybutyl vinyl ether ethoxylate (HBVE ethoxylate), have only limited stability to hydrolysis, especially in acidic media.

An object of the present invention was to provide a polymer which does not have the disadvantages mentioned above. Part of the object of the present invention was to develop a reactive alkoxylate monomer for efficient polymerization reaction. Another part of the object of the present invention was to provide such alkoxylate monomers with improved stability to hydrolysis as monomers and copolymerized with the polymers.

These and other objects are achieved by various embodiments of the present invention, particularly as outlined in the disclosure of the present invention, in particular by the unsaturated compounds of formula (I)

(Wherein,

R ¹ , R ² and R ³ are the same or different and each independently H, CH ₃ , preferably H,

R ⁴ is a linear or branched C ₁ -C ₃₀ -alkylene, preferably C ₂ -C ₁₀ -alkylene, particularly preferably C ₂ -C ₄ -alkylene, in particular -CH ₂ -CH ₂ - ,

R ^5, R ⁶ are the same or different, each independently, H, C ₁ -C ₂₀ - alkyl, C ₃ -C ₁₅ - cycloalkyl, aryl, CH ₂ -OC ₁ -C ₂₀ - alkyl, CH ₂ - OC ₂ -C ₂₀ -alkenyl, R ⁵ and R ⁶ may also together form C ₃ -C ₆ -alkylene, preferably tetramethylene, preferably H, -CH ₃ , -CH ₂ -CH ₃ , -C ₃ -C ₁₁ -alkyl, C ₁₂ -C ₂₂ -alkyl, phenyl, CH ₂ -OC ₁ -C ₁₀ -alkyl, CH ₂ -OC ₂ -C ₁₀ -alkenyl , Particularly preferably H, -CH ₃ , -CH ₂ -O-CH ₂ -CH═CH ₂ , -CH ₂ -O-2-ethylhexyl, more preferably H or -CH ₃ and particularly preferably H,

, 바람직하게는 H 또는 C₁-C₄-알킬, 특히 바람직하게는 H 이며,R ⁷ are the same or different and independently H, C ₁ -C ₄ -alkyl or

Is is alkyl, particularly preferably H, -, preferably H or C ₁ -C ₄

R ⁸ is C ₁ -C ₂₂ -alkyl, C ₂ -C ₂₂ -alkenyl, preferably C ₁₂ -C ₁₈ -alkyl, C ₁₂ -C ₁₈ -alkenyl,

n is an integer from 2 to 200, in particular from 2 to 160, preferably from 5 to 140, particularly preferably from 10 to 80 and, for example, from 20 to 30.

For purposes of the invention, expression of the C _a -C _b form shows a chemical compound or substituent having a carbon atom number of a particular. The number of carbon atoms can be selected in the entire range from a to b, including a and b, where a is greater than or equal to 1 and b is always greater than a. Another description of _a chemical compound or substituent appears through the expression of _a C _a -C _b -V form. Wherein V is a chemical compound or a substituent group such as an alkyl compound or an alkyl substituent.

Specifically, the collective terms designated for different substituents are defined as follows:

C ₁ -C ₂₂ -alkyl: straight or branched hydrocarbon residues having up to 22 carbon atoms, for example C ₁ -C ₁₀ -alkyl or C ₁₁ -C ₂₂ -alkyl, preferably C ₁ -C ₁₀ -alkyl, Alkyl, for example C ₁ -C ₃ -alkyl, such as methyl, ethyl, propyl, isopropyl or C ₄ -C ₆ -alkyl, n-butyl, sec- , Pentyl, 2-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, Dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 2-methylpropyl, or C ₇ -C ₁₀ -alkyl, such as heptyl, octyl, 2-ethylhexyl, 2, 4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, nonyl or decyl and isomers thereof.

C ₂ -C ₂₀ -alkenyl: an unsaturated, linear or branched hydrocarbon residue having from 2 to 20 carbon atoms and 1, 2 or 3, preferably 1 double bond in any desired position, such as C ₂ -C ₁₀ - alkenyl or C ₁₁ -C ₂₀ - alkenyl, preferably C ₂ -C ₁₀ - alkenyl, for example C ₂ -C ₄ - alkenyl, such as ethenyl, 1-propenyl, 2 Propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, Phenyl, 2-methyl-2-propenyl or C ₅ -C ₆ -alkenyl such as 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, Butenyl, 3-methyl-2-butenyl, 1-methyl-2-butenyl, Methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl Ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl Methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-hexenyl, Methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl- Pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, Methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, Butenyl, 1,3-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, Butenyl, 2,3-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3- 1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl- Butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl- -Ethyl-2- 1-propenyl or 1-ethyl-2-methyl-2-propenyl, and also C ₇ -C ₁₀ - isomers of alkenyl such as heptenyl, octenyl, decenyl or none carbonyl.

C ₁ -C ₃₀ -alkylene: a linear or branched hydrocarbon residue having from 1 to 30 carbon atoms, for example C ₁ -C ₁₀ -alkylene or C ₁ -C ₂₀ -alkylene, preferably C ₁ -C ₃₀ -alkylene, -C ₁₀ - alkylene, especially methylene, dimethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene.

C ₃ -C ₁₅ -cycloalkyl: monocyclic, saturated hydrocarbon group having from 3 to 15 carbon ring radicals, preferably C ₃ -C ₈ -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , Cycloheptyl or cyclooctyl, and also for example saturated or unsaturated cyclic groups such as norbornyl or norbenyl.

Aryl: a mono- to tricyclic aromatic ring system comprising 6 to 14 carbon ring members, such as phenyl, naphthyl or anthracenyl, preferably mono- to bicyclic, more preferably monocyclic, aromatic Ring system.

In a particularly preferred embodiment of the present invention, the unsaturated compound (I) has the formula (Ia)

.

.

In formula (Ia), R ³ is H or methyl, preferably H, and R ⁴ is a linear or branched C ₂ -C ₁₀ -alkylene group, preferably a linear C ₂ -C ₁₀ -group, Or branched, preferably linear C ₂ -C ₄ -alkylene. Examples thereof include 1,2-ethylene, 1,3-propylene and 1,4-butylene groups, and R ⁴ is particularly preferably a 1,2-ethylene group -CH ₂ CH ₂ -.

The group - [-O-CHR ⁵ -CHR ⁶ -] _n - in formula (Ia) is a poly (alkylene group) containing n -O-CHR ⁵ -CHR ⁶ -alkoxy groups (each alkoxy group may be the same or different) Alkoxy group. R ⁵ and R ⁶ are each independently H, methyl or ethyl, preferably H or methyl and especially H, with the proviso that the sum of the carbon atoms in the R ⁵ and R ⁶ moieties per alkoxy group is in each case 0 to 2 . In other words, the polyalkoxy group thus comprises a group selected from the group of ethoxy, propoxy and butoxy groups. When different alkoxy groups are present, they can be arranged in any sequence, for example, randomly, alternately or in blocks. In a preferred embodiment, at least 50 mol%, preferably at least 80 mol%, of the alkoxy groups are ethoxy groups. Particularly preferably, they are only ethoxy groups, i.e. R < ⁵ > and R < ⁶ >

In the formula (Ia), n is a number of from 2 to 200, preferably from 5 to 160, particularly preferably from 10 to 140, particularly preferably from 20 to 140, for example from 20 to 30. [

In another preferred embodiment of the present invention, the unsaturated compound (I) has the formula (Ib)

(Wherein n is a number of 2 to 200, preferably 5 to 160, particularly preferably 10 to 140, particularly preferably 20 to 140 and, for example, 20 to 30).

The compounds (I), in particular the compounds of formula (Ia), can be prepared by alkoxylation of the unsaturated compounds of formula (II) in particular:

.

.

For this purpose, the compound (II) is reacted with the desired amount of alkylene oxide or alkylene ether oxide, especially C ₂ - to C ₄ -alkylene oxide, particularly preferably ethylene oxide.

The performance of alkoxylation is in principle known to those skilled in the art. In this case, it is recommended that the acid be avoided as a catalyst for alkoxylation on a regular basis. In a preferred embodiment of the invention, the alkoxylation is base-catalyzed alkoxylation. To this end, the compound (II) used as a starting material can be mixed with a basic catalyst, in particular an alkali metal hydroxide, preferably potassium hydroxide, or an alkali metal alkoxide, for example potassium methoxide, in a pressure reactor.

However, alkoxylation can also be carried out by other methods. For example, it is possible to use the double hydroxide clays described in DE 4325237 A1, or it is possible to use double metal cyanide catalysts (DMC catalysts). Suitable DMC catalysts are described, for example, in DE 10243361 A1, especially in the paragraphs [0029] to [0041] and in the documents cited therein. For example, it is possible to use a catalyst of the Zn-Co type. In order to carry out the reaction, the alcohol (R ¹ ) (R ² ) -CH-CH ₂ -OH can be mixed with the catalyst and the mixture can be dehydrated as described above and reacted with the alkylene oxide . Typically, no more than 1000 ppm of catalyst is used for the mixture, and this small amount can cause the catalyst to remain in the product. The amount of catalyst may generally be less than 1000 ppm, for example less than 250 ppm.

The present invention also relates to a mixture comprising a compound of formula (I), preferably a compound of formula (Ia), particularly preferably a compound of formula (Ib). The amount of the compound of formula (I) in such a mixture may vary widely depending on the end use of the mixture. The amount of the compound of formula (I) in such a mixture is generally from 1 to 99% by weight, preferably from 10 to 95% by weight, based on the total amount of the mixture.

Such a mixture can be, for example, a mixture of different compounds of formula (I), preferably of formula (Ia), particularly preferably of formula (Ib). They may also be, for example, solvents, other monomers and / or other additives, such as stabilizers to prevent polymerization, surfactants and / or other mixtures and mixtures with additives.

In a preferred embodiment of the invention, this mixture is an aqueous solution of a compound of formula (I). One advantage of aqueous solutions of such compounds of formula (I) is their ease of handling, especially during metering.

The present invention also relates to a polymer comprising a compound of formula (I), preferably a compound of formula (Ia), particularly preferably a compound of formula (Ib) as monomers. The polymer may be a homopolymer of the compound (I) or a copolymer containing the compound (I).

In a preferred embodiment of the present invention, the polymer according to the invention comprises at least one further monomer (another monomer) different from the compound of formula (I). A number of monomers different from the compound of formula (I) may also be apparently present in the polymer.

One or more further monomers are particularly preferably monoethylenically unsaturated monomers.

Other suitable monomers include C ₂ -C ₂₄ alkenes such as ethene, propene, 1-butene, 2-butene, isobutene, diisobutene, 1-hexene, 1-heptene, , 1-decene, 1-dodecene, and 1-octadecene.

Other suitable monomers are also conjugated C ₄ -C ₁₀ dienes, such as butadiene, isoprene or chloroprene.

Another monomer, especially another monoethylenically unsaturated monomer, may especially be a monomer comprising an acid group (the acid group may also be completely or partially neutralized). They can take the form of alkali metal salts, alkaline earth metal salts, ammonium salts or salts of organic ammonium ions, among others. Monomers containing an acid group selected from the group of carboxylic acid group, sulfonic acid group, phosphoric acid group or phosphonic acid group may be preferable.

Examples of suitable other monomers having carboxylic acid groups are C ₃ -C ₁₂ monoethylenically unsaturated mono- or dicarboxylic acids, anhydrides or salts thereof, such as acrylic acid, methacrylic acid, (meth) acrylic acid anhydride, Maleic acid, maleic anhydride, fumaric acid, itaconic acid, mesaconic acid, citraconic acid or methylenemalonic acid and ammonium or alkali metal salts thereof. Acids can be used in fully or partially neutralized form.

Examples of suitable other monomers having a phosphoric acid group or a phosphonic acid group include monoethylenically unsaturated phosphonic acid esters or (poly) phosphoric acid esters and salts thereof such as hydroxyethyl, hydroxypropyl or Esters of hydroxybutyl (meth) acrylate and their alkali metal and ammonium salts, monovinyl phosphate, allylphosphonic acid, monoallyl phosphate, 3-butenylphosphonic acid, mono-3-butenylphosphate, mono (2-hydroxy-3-vinyloxypropyl) phosphate, mono (1-phosphonooxymethyl-2-vinyloxyethyl) phosphate, mono (3-allyloxy-2-hydroxypropyl) phosphate , Mono [2- (allyloxy-1-phosphonoxymethylethyl)] phosphate, 2-hydroxy-4-vinyloxymethyl-1,3,2-dioxaphosphol, 2-hydroxy- Including oxymethyl-1,3,2-dioxaphosphol . It is also possible to use salts and / or esters, in particular C ₁ -C ₈ mono-, di- and optionally trialkyl esters of monomers containing phosphoric acid and / or phosphonic acid groups.

Examples of other suitable monomers having sulfonic acid groups are monoethylenically unsaturated sulfonic acid and its salts such as vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2- acrylamidomethyldodecylsulfonic acid, 2- (meth) Acryloxyethane sulfonic acid, 3- (meth) acryloxypropane sulfonic acid, allyloxybenzenesulfonic acid, vinylbenzenesulfonic acid, vinyltoluenesulfonic acid, allylsulfonic acid, methallylsulfonic acid and the corresponding ammonium and alkali metal salts thereof.

Other suitable monomers are also esters, amides and imides of monoethylenically unsaturated mono- or dicarboxylic acids, in particular the monoethylenically unsaturated C ₃ -C ₁₂ carboxylic acids mentioned above, in particular C ₁ -C ₄₀ , Is C ₁ -C ₂₂ , particularly preferably a C ₂ -C ₁₂ ester, amide or imide. The substituent may also have another heteroatom. Here, the dicarboxylic acid may also be present in the form of their monoester or monoamide, for example as a C ₁ -C ₄ monoester. Amides and imides may be present in the form of N-mono- or optionally N, N-di-alkylated.

The esters may especially be aliphatic or cycloaliphatic ester groups, in particular esters of (meth) acrylic acid, especially (C ₁ -C ₂₂₎ , preferably C ₂ -C ₁₂ ester groups, especially (meth) acrylic acid esters. Examples of such compounds are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylate, isooctyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, (Meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-tert- butylcyclohexyl (meth) acrylate, isobornyl , 2-ethylhexyl (meth) acrylate, 2-propylheptyl (meth) acrylate or citronellol (meth) acrylate.

The ester group may also contain heteroatoms, especially oxygen and / or nitrogen atoms. Examples of such esters include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, ethyl diglycol (meth) acrylate, hydroxypropyl carbamate (Meth) acrylate, ureido (meth) acrylate, acetoacetoxyethyl (meth) acrylate, phenyl (meth) acrylate, (Meth) acrylate, hydroxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, tert-butylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and dimethylaminoethyl (meth) acrylate. Examples of preferred esters of (meth) acrylic acid include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate.

The alcohol component in the (meth) acrylic acid ester may be an alkoxylated alcohol. Here, attention is paid particularly to alkoxylated C ₁ -C ₁₈ alcohols having from 2 to 80 mol of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof. These alkoxylate example of a screen product is 3, 5, 7, 10 or 30 mol of ethylene oxide reacted with a C ₁₃ / C ₁₅ - oxo-alcohol or a mixture thereof, methyl polyglycol (meth) acrylate or (meth) acrylic acid ester .

Other examples of esters, amides or imides include monoethyl maleate, diethyl maleate, dimethyl maleate, N-substituted maleic acid imides such as N-methyl-, N-phenyl- and N-cyclohexylmaleic acid imides (Meth) acrylamide, N, N-dimethyl acrylamide, N, N-diethylacrylamide, N-isopropyl (meth) acrylamide, N- N-tert-butyl (meth) acrylamide, N-tert-octyl (meth) acrylamide, N- (1-methylundecyl) (Meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, N, N'-dicyclohexyl (Meth) acrylamidopropyl-N- (3-sulfopropyl) ammonium betaine, (meth) acrylamide, It includes a reel yl morpholine.

Monomers having amino or imino groups may also be present in the form of their quaternary salts or in the form of protonation, for example, by quaternization with methyl chloride, dimethyl sulfate or diethyl sulfate. The monomers may also be present to react with propanesultone for the corresponding betaine.

Other suitable monomers also include monomers comprising an N-vinyl group such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyl-N-methylacetamide, N-vinylimidazole, 1-vinylimidazole, a quaternary N-vinylimidazole derivative such as 1-vinyl-3-methylimidazolium chloride or methosulfate, N-vinyl-1,2,4-triazole, N-vinylcarbazole, N-vinylformamide, 2-methyl-1-vinylimidazoline.

Other suitable monomers include C ₁ -C ₂₄ esters of vinyl alcohol and monocarboxylic acids, such as vinyl formate, vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate, vinyl stearate, Examples of the acid include kojic acid such as 2,2-dimethylpropanoic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, 2-ethyl-2-methylbutanoic acid, neononanoic acid, neodecanoic acid ≪ / RTI >

Also, vinyl or allyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, vinyl cyclohexyl ether, vinyl 4-hydroxybutyl ether , Decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, hydroxybutyl vinyl ether, 2- (diethylamino) ethyl vinyl ether, 2- (di-n-butylamino) ethyl vinyl ether or methyldiglycol vinyl Ether or the corresponding allyl compound is suitable.

Also suitable are unsaturated alcohols such as 3-butene-1-ol, 2-butene-1-ol, allyl alcohol, isoprenol, prenol and methallyl alcohol.

Also suitable are alkoxylated vinyl, allyl, methallyl or isoprenyl ethers having 1-150 mol EO units or mixtures of EO and PO units.

Other suitable monomers are also N-allyl compounds, such as diallylamine, N, N-dimethyl-N, N-diallylammonium chloride.

Other suitable monomers are also alpha, beta -monoethylenically unsaturated nitriles having 3 to 10 carbon atoms, such as acrylonitrile, methacrylonitrile, fumaronitrile, and maleonitrile.

Other suitable monomers are vinyl aromatic monomers such as styrene, vinyl toluene or alpha-methyl styrene. Another styrene derivative meets the formula IV:

(Wherein R ¹¹ and R ²¹ are hydrogen or C ₁ -C ₈ -alkyl and n is 0, 1, 2 or 3). The aromatic ring may also have a heteroatom, for example 2- and 4-vinylpyridine.

Other suitable monomers are halogenated alkenes such as vinyl chloride, vinylidene chloride, trifluoroethylene, tetrafluoroethylene, and also acrolein, methacrolein.

Another monomer may also be a crosslinking monomer.

Examples of other suitable crosslinking monomers include molecules having a plurality of ethylenically unsaturated groups such as di (meth) acrylates such as ethylene glycol di (meth) acrylate, butanediol-1,4-di (meth) (Meth) acrylate of polyoxyethylene (meth) acrylate or hexanediol di (meth) acrylate or poly (meth) acrylate such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri Acrylate such as di-, tri- or tetraethylene glycol di (meth) acrylate or di-, tri- or tetrapropylene glycol di (meth) acrylate. (Meth) acrylate, isoprenyl (meth) acrylate, prenyl (meth) acrylate, dihydrodicyclopentadiene, and the like. Nyl acrylate, dicyclopentadienyl (meth) acrylate or butanediol divinyl ether. Also, di- and oligoorlyl or vinyl ethers of polyhydroxy compounds, such as ethylene glycol divinyl ether, butanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, tri Ethylene glycol divinyl ether, pentaerythritol tri- or tetraallyl ether are suitable. Oligallylamines, such as triallylamine or tetraallyl ammonium chloride, are also suitable. Also suitable are di- and oligoorlyl esters of polycarboxylic acids, such as diallyl phthalate, diallyl maleate, triallyl trimellitate, dicarboxylic acids such as succinic acid and divinyl esters of adipic acid . Also suitable are di-, tri- or oligo (meth) acrylamides such as N, N'-methylenebis (meth) acrylamide. The content of the crosslinking monomers is generally 0 to 20 mol%, preferably 0 to 10 mol%, and particularly preferably 0 to 5 mol%, based on the total number of all monomers, and particularly preferably, But does not include any crosslinking monomers.

Examples of preferred monoethylenically unsaturated monomers are styrene, butadiene, methyl (meth) acrylate, ethyl acrylate, dibutyl maleate, methyl alpha-cyanoacrylate, acrylonitrile, acrylic acid, methacrylic acid, (Meth) acrylic acid, maleic acid (anhydride), itaconic acid, vinylphosphonic acid, N-vinylpyrrolidone, N, N-dimethyl-N, N-diallylammonium chloride, acrylamide, vinylimidazole, vinyl acetate, Acrylamido-2-methylpropanesulfonic acid, and is selected from the group consisting of acrylic acid, methacrylic acid, methyl (meth) acrylate, maleic acid (anhydride), (iso) prenyl alkoxylate, (meth) Particularly preferred is butyl vinyl ether alkoxylate. Very particular preference is given to acrylic acid, methacrylic acid, (meth) acrylate, maleic acid (anhydride), (iso) prenyl alkoxylate, (meth) allylalkoxylate or hydroxybutyl vinyl ether alkoxylate.

In another preferred embodiment of the polymer according to the invention, the at least one further monomer present in the polymer, which is different from the compound of formula (I), is acrylic acid. In this case, it is particularly preferable that, in addition to the unsaturated compound of formula (I) and acrylic acid, no other monomer is present.

In another preferred embodiment of the polymer according to the invention, the at least one further monomer present in the polymer which is different from the compound of formula (I) is methacrylic acid. In this case, it is particularly preferable that, in addition to the unsaturated compound of formula (I) and methacrylic acid, no other monomer is present. The compounds of formula (I) according to the invention, unlike the corresponding vinyl ether compounds, can be readily copolymerized with (meth) acrylic acid and derivatives thereof.

In another preferred embodiment of the polymer according to the invention, the at least one further monomer present in the polymer, which is different from the compound of formula (I), is maleic acid (anhydride). In this case, it is particularly preferable that, in addition to the unsaturated compound of the formula (I) and maleic acid (anhydride), no other monomer is present.

Polymers according to the present invention can be prepared by reacting a small amount of starter or modifier (s), although they are prepared solely from monomers which are different from the compounds of formula (I) and / . ≪ / RTI >

In another preferred embodiment of the polymer according to the invention, in addition to the unsaturated compounds of formula (I), acrylic acid and methacrylic acid or acrylic acid and maleic acid (anhydride) or methacrylic acid and maleic acid (anhydride) does not exist.

In another preferred embodiment of the polymer according to the invention, in addition to the unsaturated compounds of formula (I), acrylic acid, methacrylic acid and maleic acid (anhydride), no other monomers are present.

The composition of the polymer according to the invention can vary widely depending on the particular end use. Those skilled in the art will make the appropriate choice.

The polymer according to the invention generally comprises 1 to 99.9% by weight, in particular 5 to 99.9% by weight, preferably 10 to 99.9% by weight, particularly preferably 30 to 99.5% by weight, based on the total amount of monomers in the polymer, By weight, particularly preferably from 50 to 99% by weight and particularly preferably from 55 to 96% by weight, of unsaturated compounds of the formula (I).

In a preferred embodiment of the invention, the polymer according to the invention is present in an amount of from 1 to 99.9% by weight, based on the total amount of monomers present in each case, of an unsaturated compound of formula (I), preferably compound (Ia) (Ib) and also from 99 to 0.1% by weight of another monomer of monoethylenically unsaturated, preferably from 10 to 99.9% by weight of compound (I) and from 90 to 0.1% by weight of another monoethylenically unsaturated monoethylenically unsaturated monomer Particularly preferably from 30 to 99.9% by weight of compound (I) and from 70 to 0.1% by weight of monoethylenically unsaturated further monomer, with the proviso that the compound of formula (I) and the monoethylenically unsaturated compound The total amount of the other monomers is 80% by weight or more, preferably 90% by weight or more, particularly preferably 95% by weight or more. In addition to the compounds of formula (I) and other monomers of monoethylenically unsaturated, it is very particularly preferred that no other monomers are present.

In another preferred embodiment, the polymer according to the invention comprises from 1 to 99.9% by weight, preferably from 10 to 99.9% by weight, particularly preferably from 30 to 99.9% by weight, of an unsaturated compound of formula (I) (Ia), particularly preferably compound (Ib) and another monomer in an amount of 99 to 0.1% by weight, preferably 90 to 0.1% by weight, particularly preferably 70 to 0.1% by weight, Amount is in each case relative to the total amount of monomers in the polymer and the other monomer comprises at least one selected from the following group:

(1) monoethylenically unsaturated monomers including carboxylic acid groups or anhydrides or salts thereof, such as acrylic acid, methacrylic acid, maleic acid or maleic anhydride,

(2) monoethylenically unsaturated monomers comprising phosphorous or phosphonic acid groups or salts thereof, such as esters of hydroxyethyl, hydroxypropyl or hydroxybutyl (meth) acrylates with (poly) phosphoric acid,

(3) monoethylenically unsaturated monomers including sulfonic acid groups or salts thereof, such as vinylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid,

(4) hydroxyalkyl (meth) acrylates such as hydroxyethyl acrylate or hydroxypropyl acrylate,

(5) Monoethylenically unsaturated monomers comprising polyalkoxy groups such as (iso) prenyl alkoxylate, (meth) allyl alkoxylate, hydroxybutyl vinyl ether alkoxylate or (meth) acrylate alkoxylate.

In another preferred embodiment, the polymer according to the invention comprises, in addition to one or more compounds (I), preferably (Ia), particularly preferably (Ib), two or more further different monomers, Other monoethylenically unsaturated monomers. The other monomer is preferably at least one monoethylenically unsaturated monomer containing an acid group, preferably a monomer selected from the above-mentioned groups (1), (2) and (3) and also an OH group and / or a polyalkoxy group , Preferably monomers selected from the groups (4) and (5) described above.

In this preferred embodiment the amount of compound (I), preferably compound (Ia), particularly preferably compound (Ib), is in each case in the range of from 1 to 99.9% by weight, in each case based on the total amount of all monomers in the polymer, Preferably from 10 to 99.9% by weight, particularly preferably from 30 to 99.9% by weight, and the amount of the two further monomers together is from 99 to 0.1% by weight, preferably from 90 to 0.1% by weight, particularly preferably from 70 to 0.1% Weight%.

In a preferred embodiment of the invention, the polymer according to the invention comprises from 70 to 99% by weight, preferably from 80 to 98% by weight of at least one compound (Ib) and also from 1 to 30% by weight, preferably from 2 to 20% By weight of (meth) acrylic acid.

The polymer according to the present invention has a molar mass distribution that can vary widely depending on the composition. Those skilled in the art will select suitable molar masses, depending on the intended use of the polymer. The number average molar mass M _n may be, for example, from 1000 g / mol to 1 000 000 g / mol.

In particular, the polymers according to the invention have a number average M _{n of} 1000 to 200 000 g / mol, preferably 2000 to 180 000 g / mol, particularly preferably 3000 to 150 000 g / mol, in particular 5000 to 100 000 g / mol and a molar mass distribution (molecular weight distribution) with, for example, 10 000 g / mol to 50 000 g / mol.

The present invention also provides a process for preparing a polymer.

The preparation can be carried out, in particular, by free radical polymerization of the unsaturated compounds of the formula (I), preferably (Ia), particularly preferably (Ib) and optionally also another monomer. Methods of free radical polymerization of monomers are known in principle to those skilled in the art.

The free radical polymerization can be carried out in bulk or preferably in solution. In the polymerization in solution, the choice of solvent is determined by the type of unsaturated compound (I) and optionally also another monomer, in particular by the hydrophilicity of the monomer. The polymerization can be carried out in particular in a polar solvent, preferably in an aqueous solution. It is preferable to use an aqueous solution containing at least 50% by weight of water as the solvent or solvent mixture to be used. In addition, another water-miscible solvent, such as an alcohol, may be present. The aqueous solvent preferably contains at least 70% by weight of water, particularly preferably at least 90% by weight of water. For example, the method may be performed only in water.

In order to initiate the polymerization, in principle initiated initiators for the free radical polymerization are used, in particular in the form of thermal polymerization initiators, for example peroxides or azo initiators. The polymerization temperature is selected by the person skilled in the art according to the desired result. Particularly in the polymerization in aqueous solution, temperatures of 50 ° C to 100 ° C have been found to be useful. Free radical polymerization can also be carried out by other techniques; For example, photopolymerization using a photoinitiator.

The pH during the polymerization in an aqueous solution may be selected by the person skilled in the art according to the desired result. Compound (I) according to the present invention is also stable to hydrolysis in the acid range. This differs from a similar vinyl ether compound H ₂ C = CH-OR- (AO) _x known from the prior art, which tends to hydrolyse at acidic ranges, especially at pH values of less than 3. This significantly reduces their availability. The compounds (I) according to the invention can be used in combination with other monomers, optionally in the presence of free radicals in aqueous solution, in an acidic pH range, particularly advantageously at a pH of 1 to 6, preferably of 1 to 5 and in particular of pH 1 to 3 Can be polymerized.

The free radical polymerization can be carried out, for example, by a batch process, a semi-batch process or by a continuous process. Suitable continuous processes are described, for example, in WO 2009/100956 A2.

Free radical polymerization in an aqueous solution of an unsaturated compound (I), preferably the compound (Ia), particularly preferably the compound (Ib) and another monomer, especially an acid group, Various techniques can be used.

In one embodiment of the present invention, the monomer as it is or the mixture in the solution is initially charged in the reaction vessel, and then the polymerization is started by, for example, adding a thermal polymerization initiator and raising the temperature.

In another embodiment of the present invention, the solution of the unsaturated compound (I) and optionally also some of the other monomers and some of the thermal polymerization initiators are initially charged to the reaction vessel. In this embodiment, up to 25 wt.% Of another monomer must be initially charged. The remaining amount of another monomer and also the remaining amount of initiator is added after the start of the polymerization, especially after heating to the polymerization temperature. In this case, the solution of the further monomer and the solution of the initiator are preferably continuously metered in the reaction vessel.

In a preferred embodiment of the present invention, the unsaturated compound (I) and another monomer are metered slowly in a polymerization reactor containing a certain amount or more of a solvent, especially an aqueous solvent.

In this embodiment, only a portion of the unsaturated compound (I), another monomer and also an initiator are initially charged into the reaction vessel, wherein the amount of monomer initially charged is 25% by weight of the total intended amount of monomers, Should not exceed 10% by weight and the molar ratio of the initially charged monomers should be selected to correspond to the intended ratio in the polymer. The deviation should generally be not more than +/- 20%, preferably not more than +/- 10% of the intended ratio. The proportion of initially charged monomers is particularly preferably corresponding to the desired monomer proportion.

Polymerization of some initially charged monomers starts early. This can be done by heating the batch to the desired polymerization temperature. Alternatively, an initiator, such as a redox initiator, may be added to initiate the polymerization in advance at room temperature. When an initiator is added to the monomer, polymerization is initiated. After the start, the unsaturated compound (I) and another monomer are preferably added as a solution. In this case, the monomer may be added separately, or a mixture of the unsaturated compound (I) and another monomer, preferably a solution of the unsaturated compound (I) and another monomer in a suitable solvent may also be added. In the latter case, the ratio of the unsaturated compound (I) to another monomer is naturally fixed, but the ratio of the first case may also vary during the polymerization. The initiator is likewise metered in as a solution in a suitable solvent.

Here, the rate of addition during addition of the unsaturated compounds (I) and the further monomers should be chosen so as to avoid too much excess of the unconjugated unsaturated compound (I) or another monomer of the unpolymerized in each case in the reaction vessel. Excess unreacted unsaturated compounds (I) must be avoided in particular. The molar ratio of the unsaturated compound (I) / another monomer is referred to as x in the following. The rate of addition of the monomers should preferably be selected so that the molar ratio of monomers fed to the reactor does not deviate from the intended ratio by +/- 20%, preferably +/- 10% or less, wherein the total amount of monomers is clearly It should correspond to the desired value.

Embodiments of the polymerization described above form copolymers with particularly good performance properties. These advantages are particularly remarkable in the copolymerization of the unsaturated compound (I) with another monomer having another acid group such as acrylic acid in an aqueous solution. This is also described in more detail in the Example section. Although it is not desired to commit to a particular theory, it is believed that the effect is due to the fact that the monomers are particularly uniformly incorporated in the preferred embodiments.

The present invention also provides a process for preparing a polymer as follows:

a. Free radical polymerization of monomers comprising unsaturated compounds of formula (II) and

b. Step a. Polymer-like reaction of a compound of formula < RTI ID = 0.0 > (III) <

(Wherein the symbols and indices have the above-mentioned meanings)

.

The present invention also relates to a cement admixture, a crushing aid in the manufacture of cement, an additive for hydraulic binder, a concrete plasticizer, a plastic (e.g. polyvinyl alcohol, polyvinyl butyraldehyde), a rubber or latex (e.g. styrene / butadiene rubber- / Butadiene rubber-NBR), as associative thickeners, as antioxidants, or to the use of polymers according to the invention for preparing polyether siloxanes.

The invention also relates to a mixture comprising a polymer according to the invention.

The polymer according to the invention is preferably a concrete plasticizer which serves to plasticize the concrete, preferably as a mixture. Such a mixture is generally a mixture of a plasticizer and a binder, optionally in combination with a concrete plasticizer of the lignin sulfonate type and / or a beta-naphthalenesulfonic acid-formaldehyde co-condensate, a deacidising agent, an air-entraining additive, And a fluidizing agent of the carboxylate ether type.

Particularly suitable for use as concrete plasticizers are copolymers comprising unsaturated compounds (I) and also one or more further monomers, especially one or more monoethylenically unsaturated monomers. The unsaturated compounds (I) for this use are preferably compounds (Ia), particularly preferably compounds (Ib) wherein n in formula (Ib) is preferably from 20 to 140, especially from 20 to 60, Is from 20 to 30). Examples of other monomers particularly suitable for use as concrete plasticizers are acrylic acid, methacrylic acid, maleic anhydride, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyethyl (meth) Phosphate, hydroxypropyl (meth) acrylate phosphate.

Suitable copolymers for use as concrete plasticizers generally comprise from 55 to 99.9% by weight of unsaturated compounds (I) and from 0.1 to 45% by weight of another monomer of monoethylenically unsaturated (unsaturated compounds (I) and monoethylene The total amount of the other unsaturated monomers, especially those mentioned above, is not less than 90% by weight, particularly preferably not less than 95% by weight). In addition to the compounds of formula (I) and other monomers of monoethylenically unsaturated, it is very particularly preferred that no other monomers are present. For this use, the number average molecular weight M _n is preferably from 1000 g / mol to 100 000 g / mol, in particular from 5000 g / mol to 100 000 g / mol and, for example, from 10 000 g / mol to 40 000 g / mol.

Another preferred mixture is a mixture of a polymer according to the invention and another polymer, preferably an elastomer. Examples of such polymers are rubber, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl butyraldehyde.

When a rubber is selected as the polymer, such a rubber is preferably an SBR rubber such as S-SBR rubber or E-SBR rubber, BR rubber, EPM rubber, EPDM rubber, SB rubber, IIR rubber, , Preferably rubber types selected from the group consisting of SBR rubbers and NBR rubbers.

The present invention provides hydrolytically stable reactive alkoxylate monomers that can be efficiently converted into hydrolytically stable polymers.

The present invention will be described in detail with reference to examples, but these examples do not limit the gist of the present invention.

Example:

VME: vinyl mercaptoethanol H ₂ C = CH-S-CH ₂ CH ₂ OH

HBVE: hydroxybutyl vinyl ether H ₂ C = CH-O-CH ₂ CH ₂ CH ₂ CH ₂ OH

How to measure:

Number of OH:

The OH number (OHN) is a measure of the alcohol group present in the sample. The measurement is carried out by esterifying the alcohol group with excess acetic anhydride. After hydrolysis of the unreacted acetic anhydride, the remaining free acetic acid is titrated with KOH. The OH number data is expressed in units of mg KOH / g sample. Therefore, the OH number corresponds to the amount of KOH in "mg", which corresponds to the amount of acetic acid associated with acetylation of 1 g of material.

PEG content:

The polyethylene glycol content is defined as the ratio of PEG in the nonionic surfactant and EO adduct, which can be measured by thin layer chromatography. This is referred to as g per 100 g. The polyethylene glycol is separated from the oxyethylate in the material spot by thin layer chromatography using an immediately available HPTLC plate and quantified by the position curve measurement after derivatization with a Dragendorff reagent. Evaluation is performed after calibration with the PEG standard (PEG 1000).

GPC measurement

(For all experiments except for 5a to 5g and for comparative experiments 5a to 5c):

column:

Columns from the following PSS Mainz were connected in series and maintained at 35 [deg.] C:

· PSS Suprema pre-column

PSS Suprema 30 Å, 10μ 8 × 300 mm

PSS Suprema 1000 Å, 10μ 8 × 300 mm

PSS Suprema 3000 Å, 10μ 8 × 300 mm

Column material:

Modified acrylate copolymer network.

Eluent:

Phosphate buffer pH 9.7

0.0239 mol / L disodium hydrogen phosphate (dihydrate),

adjusted to pH 9.7, NaOH 2 mol / L,

0.5 g / L sodium azide.

The sample is diluted with the eluent.

Device / Software:

Agilent 1100 system with ChemStation, evaluation using PSS WinGPC Unity.

Condition:

Sample dilution:

1.5 mL eluent + 10 μL acetone (internal standard) + 20 μL sample (up to 50% solution, the higher the concentration)

Injection: 50 μL, with needle wash,

Flow rate: 0.8 mL / min,

Execution time: 60 min,

Detector: RID (Agilent G1362A), 35 ° C.

correction:

Calibration standards from PSS: polyethylene glycol (PEG), polyethylene oxide (PEO) for high molar mass. Internal standard for compensation of flow rate changes: acetone.

GPC methods for Experiments 5a-5g and Comparative Experiments 5a-5c (see Table 4):

: Column combinations: OHpak SB-G from Shodex, Japan, OHpeak SB 804 HQ and OHpak SB 802.5 HQ; Eluent: HCO ₂ NH ₄ (0.05 mol / l) in 80 vol% aqueous solution and 20 vol% acetonitrile; Injection volume 100 [mu] l; Flow rate 0.5 ml / min). Calibration was performed to determine the average molar mass using a linear polyethylene glycol standard. The polymer peak is normalized to a relative height of 1 as a measure of conversion and the peak height of the unreacted macromonomer / PEG-containing oligomer is used as a measure of the residual monomer content.

Example 1: Preparation of alkoxylate of S-vinylthioalkanol

Example 1a:

Reaction:

A 2 L autoclave was charged with 104 g (1.00 mol) of vinyl mercaptoethanol and 2.18 g (19.4 mmol KOH) aqueous solution of potassium hydroxide (50% by weight) at 70 DEG C and water Respectively. Subsequently, nitrogen was flushed into the autoclave and the temperature was raised to 130 캜. 440 g (10.0 mol) of ethylene oxide was added over 4 h. The resulting reaction mixture was then stirred at 130 캜 for 10 h, cooled to 100 캜 and then removed from the volatile components under reduced pressure.

572 g of a brown liquid were obtained.

OHN = 102.5 mg KOH / g (theory 103.0 mg KOH / g)

Example 1b:

Reaction:

A 2 L autoclave was charged with an aqueous potassium hydroxide solution (50 wt%) of 164 g (0.30 mol) of vinyl mercaptoethanol ^* 10EO (Example 1a) and 686 mg (6.11 mmol KOH) Lt; / RTI > for 2 h. Subsequently, nitrogen was flushed into the autoclave and the temperature was raised to 130 캜. 172 g (3.90 mol) of ethylene oxide was added over 1.5 h. The resulting reaction mixture was then stirred at 130 캜 for 8 h, cooled to 100 캜 and then removed from the volatile components under reduced pressure.

337 g of a brown solid were obtained.

OHN = 55.6 mg KOH / g (theory 50.2 mg KOH / g); PEG content = 10.5% by weight.

Example 1c:

Reaction:

A 2 L autoclave was charged with 52.1 g (0.50 mol) of vinylmercaptoethanol and 410 mg (1.87 mmol KOMe) of a methanolic potassium methoxide solution (32% by weight in methanol) at 65 ° C and a solution of 2 h < / RTI &gt; Subsequently, nitrogen was flushed into the autoclave, and the temperature was raised to 120 캜. 528 g (12.0 mol) of ethylene oxide was added over 4 h. The resulting reaction mixture was then stirred at 120 캜 for 10 h, cooled to 100 캜 and then removed from the volatile components under reduced pressure.

606 g of a brown solid were obtained.

OHN = 47.5 mg KOH / g (theory 48.8 mg KOH / g), PEG content: < 1 wt%

Example 1d:

Reaction:

A 2 L autoclave was charged with 104 g (1.00 mol) of vinyl mercaptoethanol and 289 mg (90%, 4.50 mmol KOH) of KOH flake in 416 g of toluene at 60 캜 and flushed with nitrogen. The temperature was then raised to 120 占 폚. 1057 g (24.0 mol) of ethylene oxide was added over 13 h. The resulting reaction mixture was then stirred at 120 캜 for 10 h, cooled to 105 캜 and then removed from the volatile components under reduced pressure.

1181 g of a light brown solid were obtained.

OHN = 50.6 mg KOH / g (theoretical 48.8 mg KOH / g), PEG content: < 1 wt%

Example 1e:

Reaction:

A 2 L autoclave was charged with 104 g (1.00 mol) of vinylmercaptoethanol and 641 mg (2.97 mmol KOMe) of a methanolic potassium methoxide solution (32% by weight in methanol) at 60 캜 and a solution of 2 h < / RTI &gt; Subsequently, nitrogen was flushed into the autoclave and the temperature was raised to 130 캜. 581 g (10.0 mol) of propylene oxide was added over 10 h. The resulting reaction mixture was then stirred at 130 캜 for 10 h, cooled to 100 캜 and then removed from the volatile components under reduced pressure.

629 g of a dark brown solid were obtained.

OHN = 88.0 mg KOH / g (theory 81.9 mg KOH / g)

Example 1f:

Reaction:

A 2 L autoclave was charged with 188 g (275 mmol) of aqueous solution of potassium hydroxide (50 wt%) of vinyl mercaptoethanol ^* 10PO (Example 1e) and 1.85 g (16.6 mmol KOH) at 100 占 폚, Lt; / RTI &gt; for 2 h. Subsequently, nitrogen was flushed into the autoclave, and the temperature was raised to 120 캜. 396 g (9.00 mol) of ethylene oxide was added over 6 h. The resulting reaction mixture was then stirred at 120 &lt; 0 &gt; C for 5 h, cooled to 90 &lt; 0 &gt; C and then removed from the volatiles under reduced pressure.

597 g of a light brown solid were obtained.

OHN = 31.8 mg KOH / g (theory 28.8)

Example 1g:

Reaction:

A 50% by weight aqueous solution of potassium hydroxide (68.4 g, 0.10 mmol) of vinylmercaptoethanol ^* 10PO (Example 1e) and 0.62 g (5.52 mmol KOH) was charged to a 2 L autoclave at <Lt; / RTI &gt; for 2 h. Subsequently, nitrogen was flushed into the autoclave, and the temperature was raised to 120 캜. 550 g (12.5 mol) of ethylene oxide was added over 6 h. The resulting reaction mixture was then stirred at 120 &lt; 0 &gt; C for 5 h, cooled to 90 &lt; 0 &gt; C and then removed from the volatiles under reduced pressure.

610 g of a brown solid were obtained.

OHN = 12.2 mg KOH / g (theory 9.2), PEG content: 1.4 wt%

Example 1h:

Reaction:

A 2 L autoclave was charged with 46.7 g (448 mmol) of vinyl mercaptoethanol and 120 mg (1.71 mmol) of potassium methoxide in 100 mL of toluene at 60 占 폚 and flushed with nitrogen. The temperature was then raised to 120 占 폚. 1321 g (30.0 mol) of ethylene oxide was added over 20 h. The resulting reaction mixture was then stirred at 120 캜 for 10 h, cooled to 100 캜 and then removed from the volatile components under reduced pressure.

1396 g of a light brown solid were obtained.

OHN = 21.2 mg KOH / g (theory 18.4 mg KOH / g), PEG content: 1.4 wt%

Example 1i:

Reaction:

To a 2 L autoclave, 23.4 g (224 mmol) of vinyl mercaptoethanol and 120 mg (1.71 mmol) of potassium methoxide were charged in 50 mL of toluene at 60 占 폚 and flushed with nitrogen. The temperature was then raised to 120 占 폚. 1332 g (30.2 mol) of ethylene oxide was added over 36 h. The resulting reaction mixture was then stirred at 12O &lt; 0 &gt; C for 12 h, cooled to 100 &lt; 0 &gt; C and then removed from the volatiles under reduced pressure.

1388 g of a light brown solid were obtained.

OHN = 12.1 mg KOH / g (theoretical 9.3 mg KOH / g), PEG content: 2.0 wt%

Comparative Example 1j:

Manufacture of HBVE-24 EO

The procedure was as in Example 1c, and only the corresponding amount of HBVE was used instead of VME.

Comparative Example 1k:

Manufacture of HBVE-67 EO

The procedure was the same as in Example 1h, and only the corresponding amount of HBVE was used instead of VME.

Comparative Example 1 l:

Manufacture of HBVE-135 EO

The procedure was as in Example 1i, and only the corresponding amount of HBVE was used instead of VME.

Example 2: Preparation of Polymer, Method (A)

In process (A), VME or HBVE alkoxylate is initially charged for polymerization.

Example 2a:

89 wt% Copolymer of VME-23EO and 11 wt% acrylic acid

Polymerization at pH 2-3 (starting azo)

35.6 g of VME ethoxylate (23EO) according to Example Ib was dissolved in 63.5 g of water in a glass reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen line and addition line. A portion (1.1 g) of Solution A (4.4 g of acrylic acid dissolved in 18.4 g of water) and a portion (2 g) of Solution B (1.6 g of 2,2'-azobis [2 - (2-imidazolin-2-yl) propane] dihydrochloride (Wako VA-44). The polymerization was started by heating the solution to 70 캜 under nitrogen, and then the remaining amount of solutions A and B was added, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 70 &lt; 0 &gt; C for 2 h.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

Example 2b:

The procedure was the same as in Example 2a, only reducing the amount of initiator from 1.6 g to 1.2 g.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

Example 2c:

The procedure was the same as in Example 2a, only reducing the amount of initiator from 1.6 g to 0.8 g.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

Comparative Example 2a:

89 wt% Copolymer of HBVE-24EO and 11 wt% acrylic acid

35.6 g of HBVE-24EO according to Comparative Example 1i were dissolved in 63.5 g of water in a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen line and an addition line. A portion (1.1 g) of Solution A (4.4 g of acrylic acid dissolved in 18.4 g of water) and a portion (2 g) of Solution B (1.6 g of 2,2'-azobis [2 - (2-imidazolin-2-yl) propane] dihydrochloride (Wako VA-44). The polymerization was started by heating the solution to 70 캜 under nitrogen, and then the remaining amount of solutions A and B was added, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 70 &lt; 0 &gt; C for 2 h.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

Comparative Example 2b:

The procedure was the same as in Example 2, only reducing the amount of initiator from 1.6 g to 1.2 g.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

Comparative Example 2c:

The procedure was the same as in Example 2, only reducing the amount of initiator from 1.6 g to 0.8 g.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

GPC measurements of the reaction products from Example 2a and Comparative Example 2a showed additional very apparent low molecular weight peaks in the case of HBVE-24EO (Comparative Example 2a). In the case of HBVE ethoxylate, a large proportion of the monomers were hydrolyzed during the polymerization.

Further, in the 1 H-NMR measurement of Comparative Examples 2a, 2b and 2c, the vinyl compound was no longer observed.

Example 2d:

85 wt% Copolymer of VME-23EO and 15 wt% Na acrylate

Polymerization at pH 7-8 (starting azo)

34.0 g of VME ethoxylate-23 EO according to Example 1b was dissolved in 63.5 g of water in a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen line and an addition line. A solution of Part A (1.2 g) of Solution A (6.0 g of sodium acrylate in 18.4 g of water) and a portion (2 g) of Solution B (1.6 g of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (Wako VA-44)) was added. The polymerization was started by heating the solution to 70 캜 under nitrogen, and then the remaining amount of solutions A and B was added, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 70 &lt; 0 &gt; C for 2 h.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

Comparative Example 2d:

85 wt% Copolymer of HBVE-24EO and 15 wt% Na acrylate

Polymerization at pH 7-8 (starting azo)

34.0 g of HBVE-24 EO according to Example 1i was dissolved in 63.5 g of water in a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen line and an addition line. A solution of Part A (1.2 g) of Solution A (6.0 g of sodium acrylate dissolved in 18.4 g of water) and a portion (2 g) of Solution B (1.6 g of 2,2'-azobis [ 2- (2-imidazolin-2-yl) propane] dihydrochloride (Wako VA-44). The polymerization was started by heating the solution to 70 캜 under nitrogen, and then the remaining amount of solutions A and B was added, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 70 &lt; 0 &gt; C for 2 h.

Hydrolysis of HBVE ethoxylate was not observed at neutral pH. The ¹ H-NMR measurement of the polymer showed that about 8% of the HBVE ethoxylate used was not polymerized. The molar mass of the HBVE ethoxylate / acrylic acid copolymer was clearly lower than that of the VME ethoxylate-acrylic acid copolymer.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

Example 2e:

89 wt% Copolymer of VME-23EO and 11 wt% acrylic acid

Polymerization at pH 1.9 (peroxide starting material)

42.7 g of VME ethoxylate-24EO according to Example 1d were dissolved in 38.8 g of water in a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen line and an addition line. The solution was heated to 95 占 폚 under nitrogen and the addition of solution A (5.3 g of acrylic acid dissolved in 41.4 g of water) and B (1.9 g of sodium peroxodisulfate dissolved in 31.4 g of water) At this time, Solution A was added over 4 hours, and Solution B was added over 5 hours. The reaction mixture was then stirred at 95 &lt; 0 &gt; C for 2 h.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

Comparative Example 2e:

89 wt% Copolymer of HBVE-24EO and 11 wt% acrylic acid

Polymerization at pH 1.9

42.7 g of HBVE-24EO according to Comparative Example lj were dissolved in 38.8 g of water in a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen line and an addition line. The solution was heated to 95 캜 under nitrogen and the addition of solution A (5.3 g of acrylic acid dissolved in 41.4 g of water) and B (1.9 g of sodium peroxodisulfate dissolved in 31.4 g of water) At this time, Solution A was added over 4 hours, and Solution B was added over 5 hours. The reaction mixture was then stirred at 95 &lt; 0 &gt; C for 2 h.

Strong hydrolysis of HBVE ethoxylate was observed. In GPC, a large peak was observed at low molar mass.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

Example 2f: bulk polymerization

89 wt% Copolymer of VME-24EO and 11 wt% acrylic acid

71.2 g of VME-24EO according to Example 1d and 2.4 g of 2-mercaptoethanol were initially charged in a glass reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen line and addition line. The mixture was heated to 85 占 폚 under nitrogen and the addition of 8.7 g of acrylic acid and 3.2 g of tert-butyl peroctoate was started, at which time acrylic acid was added over 3 hours and the initiator was added over 4 hours. The reaction mixture was then stirred at 85 &lt; 0 &gt; C for 4 h.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

Comparative Example 2f:

89 wt% Copolymer of HBVE-24EO and 11 wt% acrylic acid

71.2 g HBVE-24 EO and 2.4 g 2-mercaptoethanol according to Comparative Example lj were initially charged in a glass reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen line and addition line. The mixture was heated to 85 占 폚 under nitrogen and the addition of 8.7 g of acrylic acid and 3.2 g of tert-butyl peroctoate was started, at which time acrylic acid was added over 3 hours and the initiator was added over 4 hours. The reaction mixture was then stirred at 85 &lt; 0 &gt; C for 4 h.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

Polymers according to the invention can also be prepared in bulk (no solvent). In the case of bulk polymerization, the monomers are treated with an azo initiator. For example, bulk copolymerization of VME ethoxylate with acrylic acid is also possible using peroctoate as initiator at 85 &lt; 0 &gt; C. Further, for the bulk polymerization, a modifier such as mercaptoethanol or mercaptopropionic acid may be used.

Example 2g: Polymerization of long chain VME ethoxylate

81 wt% Copolymer of VME-67EO and 19 wt% acrylic acid

Polymerization at pH 2-3 (starting azo)

32.6 g of VME ethoxylate (67EO) according to Example 1h were dissolved in 63.5 g of water in a glass reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen line and addition line. A portion (1.3 g) of solution A (7.6 g of acrylic acid dissolved in 18.4 g of water) and a part (2 g) of solution B (1.6 g of 2,2'-azobis [2 - (2-imidazolin-2-yl) propane] dihydrochloride (Wako VA-44). The polymerization was started by heating the solution to 70 캜 under nitrogen, and then the remaining amount of solutions A and B was added, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 70 &lt; 0 &gt; C for 2 h.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

Comparative Example 2g:

81 wt% Copolymer of HBVE-67EO and 19 wt% acrylic acid

Polymerization at pH 2-3 (starting azo)

32.4 g of HBVE ethoxylate (67EO) according to Comparative Example 1k was dissolved in 57.6 g of water in a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen line and an addition line. A portion (1.6 g) of solution A (7.6 g of acrylic acid dissolved in 24.0 g of water) and a part (2 g) of solution B (1.6 g of 2,2'-azobis [2 - (2-imidazolin-2-yl) propane] dihydrochloride (Wako VA-44). The polymerization was started by heating the solution to 70 캜 under nitrogen, and then the remaining amount of solutions A and B was added, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 70 &lt; 0 &gt; C for 2 h.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

GPC measurements of the reaction products from Example 2g and Comparative Example 2g showed additional very apparent low molecular weight peaks in the case of HBVE-24EO (Comparative Example 2g). In the case of HBVE ethoxylate, a large proportion of the monomers were hydrolyzed during the polymerization. Further, in the &lt; 1 &gt; H-NMR measurement of Comparative Example 2g, the vinyl compound was observed again.

Example 2h:

81 wt% Copolymer of VME-135EO and 19 wt% acrylic acid

Polymerization at pH 2-3 (starting azo)

32.3 g of VME ethoxylate (135EO) was dissolved in 63.5 g of water in a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen line and an addition line. Some (1.3 g) of Solution A (7.7 g of acrylic acid dissolved in 18.4 g of water) and a portion (2 g) of Solution B (1.6 g of 2,2'-azobis [2 - (2-imidazolin-2-yl) propane] dihydrochloride (Wako VA-44). The polymerization was started by heating the solution to 70 캜 under nitrogen, and then the remaining amount of solutions A and B was added, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 70 &lt; 0 &gt; C for 2 h.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

Comparative Example 2h:

81 wt% Copolymer of HBVE-135EO and 19 wt% acrylic acid

Polymerization at pH 2-3 (starting azo)

32.3 g of HBVE ethoxylate (135EO) according to Comparative Example l was dissolved in 57.6 g of water in a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen line and an addition line. A portion (1.6 g) of solution A (7.7 g of acrylic acid dissolved in 24.0 g of water) and a part (2 g) of solution B (1.6 g of 2,2'-azobis [2 - (2-imidazolin-2-yl) propane] dihydrochloride (Wako VA-44). The polymerization was started by heating the solution to 70 캜 under nitrogen, and then the remaining amount of solutions A and B was added, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 70 &lt; 0 &gt; C for 2 h.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

Example 3: Preparation of Polymer, Method (B)

In process (B), the VME or HBVE alkoxylate is not initially charged for polymerization and is added slowly during the polymerization.

Example 3a:

A copolymer of 89 wt% VME-23EO and 11 wt% acrylic acid (molar ratio 1: 2)

Polymerization at pH 2.8 (peroxide starting material)

A solution B (0.8 g (75 g) of a solution A (66.6 g of VME-23EO according to Example Ib, 4.4 g of acrylic acid and 18 g of water) and a portion (1.9 g) of water % Solution of tert-butyl perpivalate and 36 g of isopropanol) were initially charged in a glass reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen line and addition line. The initial charge was heated to 75 占 폚 under nitrogen, and the remaining amount of solutions A and B was added to initiate polymerization, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 75 &lt; 0 &gt; C for 2 h. Isopropanol was distilled off.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 2.

Example 3b:

89 wt% Copolymer of VME-23EO and 11 wt% acrylic acid

Polymerization at pH 2.6 (starting azo)

A solution B (1.6 g of 2 &lt; RTI ID = 0.0 &gt; g) &lt; / RTI &gt; of 66 g water, some (2.9 g) solution A (35.6 g VME-23EO according to Example Ib, 4.4 g acrylic acid and 18 g water) (Wako VA-44) and 168 g of water) were initially charged in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen line and a condenser, And charged into a glass reactor equipped with an addition line. The initial charge was heated to 70 캜 under nitrogen and the addition of the remaining amount of solutions A and B was started, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 70 &lt; 0 &gt; C for 2 h.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 2.

Comparative Example 3a:

86 wt% Copolymer of HBVE-24EO and 14 wt% Na acrylate

Polymerization at pH 8.5 (peroxide starting material)

288.7 g of water, a solution B (14 g) of solution A (150.8 g of HBVE-24 EO according to Comparative Example 1i, 80.6 g of 30% acrylic acid Na salt solution and 48.5 g of water) (3.5 g (75% solution) of tert-butyl perpivalate and 131.2 g of isopropanol) were initially charged in a glass reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen line and addition line. The initial charge was heated to 75 占 폚 under nitrogen, and the addition of the remaining amounts of solutions A and B was started, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 75 &lt; 0 &gt; C for 2 h. The reaction mixture was kept constant at pH 7.5-8.0. Then, isopropanol was distilled off.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 2.

Comparative Example 3b

86 wt% Copolymer of HBVE-24EO and 14 wt% Na acrylate

Polymerization at pH 2-3 (starting azo)

A solution B of 252 g of water, part (14 g) of solution A (150.8 g of HBVE-24 EO according to Example li, 80.6 g of 30% acrylic acid Na salt solution and 48.5 g of water) Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (Wako VA-44) and 168 g of water) were initially charged in an agitator, a reflux condenser, A glass reactor equipped with a thermometer, nitrogen line and addition line was charged. The initial charge was heated to 70 캜 under nitrogen and the addition of the remaining amount of solutions A and B was started, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 70 &lt; 0 &gt; C for 2 h. The reaction mixture was kept constant at pH 7.5-8.0.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 2.

Example 3c:

97 wt% Copolymer of VME-135EO and 3 wt% Na acrylate

Polymerization at pH 9.4 (peroxide starting material)

A solution B of 39.4 grams of water, some (4.4 grams) of solution A (36.4 grams of VME-135 EO according to Example 1h, 3.7 grams of 30% acrylic acid Na salt solution and 48 grams of water) (0.75 g (75% solution) of tert-butyl perpivalate and 22 g of isopropanol) were initially charged in a glass reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen line and addition line. The initial charge was heated to 75 占 폚 under nitrogen, and the addition of the remaining amounts of solutions A and B was started, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 75 &lt; 0 &gt; C for 2 h. Isopropanol was distilled off.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 2.

Example 3d:

97 wt% Copolymer of VME-135EO and 3 wt% Na acrylate

Polymerization at pH 8.6 (starting azo)

45 g of water, a solution B (4.4 g) of solution A (36.7 g of VME-135 EO according to Example 1h, 3.7 g of 30% acrylic acid Na salt solution and 48 g of water) and part (0.88 g) (0.75 g of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (Wako VA-44) and 17 g of water) were initially charged in a stirrer, A glass reactor equipped with a thermometer, nitrogen line and addition line was charged. The initial charge was heated to 70 캜 under nitrogen and the addition of the remaining amount of solutions A and B was started, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 70 &lt; 0 &gt; C for 2 h.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 2.

Comparative Example 3c :

94 wt% Copolymer of HBVE-135EO and 6 wt% Na acrylate

Polymerization at pH 7.7 (peroxide starting material)

A solution B of 238.7 grams of water, some (14.0 grams) of solution A (164.9 grams of HBVE-135EO according to Comparative Example lj, 33.7 grams of 30 percent acrylic acid Na salt solution and 131.4 grams of water) (3.5 g (75% solution) of tert-butyl perpivalate and 131.2 g of isopropanol dissolved) were initially charged in a glass reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen line and addition line. The initial charge was heated to 75 占 폚 under nitrogen, and the addition of the remaining amounts of solutions A and B was started, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 75 &lt; 0 &gt; C for 2 h. The reaction mixture was kept constant at pH 7.5-8.0. Then, isopropanol was distilled off.

The data on the synthesis and also the Mn, Mw and PDI of the obtained polymer are shown in Table 2.

Example 4:

Polymerization of VME ethoxylate and methacrylic acid

Example 4a:

87 wt% Copolymer of VME-24EO and 13 wt% Na methacrylate

Polymerization at pH 7.5-8.0 (starting azo), Method (A)

A solution B (1.6 grams) of A (17.2 grams of 30% solution of Na salt of methacrylic acid and 12 grams of water) and a portion (2.0 grams) of 57 grams of water, 34.8 grams of VME-24EO, Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (Wako VA-44) and 38.4 g of water) were initially charged in an agitator, a reflux condenser, Line and an addition line. The initial charge was heated to 70 캜 under nitrogen and the addition of the remaining amount of solutions A and B was started, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 70 &lt; 0 &gt; C for 2 h.

The results are shown in Table 3.

Example 4b:

82 wt% VME-23EO and 18 wt% Na methacrylate Copolymer

Polymerization at pH 7.5-8.0 (peroxide starting material), Method (A)

A solution B (1.6 grams) of 70 g water, 33 g VME-23EO, solution A (24 g of a 30% solution of Na salt of methacrylic acid and 20 g of water and some 0.8 g) (75% solution) of tert-butyl perpivalate and 14.4 g of isopropanol) were initially charged in a glass reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen line and addition line. The initial charge was heated to 75 占 폚 under nitrogen, and the addition of the remaining amounts of solutions A and B was started, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 75 &lt; 0 &gt; C for 2 h. Isopropanol was distilled off.

The results are shown in Table 3.

Example 4c:

87 wt% Copolymer of VME-23EO and 13 wt% Na methacrylate

Polymerization at pH 2.5-3.0 (peroxide starting material), Method (A)

Solution B (1.6 g (75%)) of 70 g of water, 35 g of VME-23 EO, some (2.0 g) of Solution A (5.2 g of methacrylic acid dissolved in 36 g of water) Butyl perpivalate and 14.4 g of isopropanol) were initially charged in a glass reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen line and addition line. The initial charge was heated to 75 占 폚 under nitrogen, and the addition of the remaining amounts of solutions A and B was started, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 75 &lt; 0 &gt; C for 2 h. Isopropanol was distilled off.

The results are shown in Table 3.

Example 4d:

89 wt% VME-23EO and 11 wt% Na methacrylate Copolymer

7.5-8.0 (azo starting material), Method (B)

A solution B (1.6 g of 2,2 ') of 66 g of water, a solution A (35.6 g of VME-23EO, 4.4 g of methacrylic acid and 18 g of water) and part (1.9 g) of Part A (2.9 g) (Wako VA-44) and 36 g of water) were initially charged in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen line and an addition line And filled in a glass reactor equipped. The initial charge was heated to 70 캜 under nitrogen and the addition of the remaining amount of solutions A and B was started, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 70 &lt; 0 &gt; C for 2 h.

The results are shown in Table 3.

Example 4e:

89 wt% VME-23EO and 11 wt% Na methacrylate Copolymer

Polymerization at pH 7.5-8.0 (peroxide starting material), Method (B)

A solution B (0.8 g (75% solution) of 66 g of water, a solution A (35.6 g of VME-23EO, 4.4 g of methacrylic acid and 18 g of water) and part Of tert-butyl perpivalate and 36 g of isopropanol) were initially charged in a glass reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen line and an addition line. The initial charge was heated to 75 占 폚 under nitrogen, and the addition of the remaining amounts of solutions A and B was started, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 75 &lt; 0 &gt; C for 2 h. Isopropanol was distilled off.

The results are shown in Table 3.

Comparative Example 4f:

87 wt% HBVE-23EO and 13 wt% Na methacrylate Copolymer

Polymerization at pH 7.5-8.0 (starting azo), Method (A)

Reaction:

A solution B (1.6 grams) of 57.6 grams of water, 35 grams of HBVE-24EO, solution A (17 grams of a 30% solution of sodium methacrylate Na salt solution and 12 grams of water) and part Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (Wako VA-44) and 38.4 g of water) were initially charged in an agitator, a reflux condenser, Line and an addition line. The initial charge was heated to 70 캜 under nitrogen and the addition of the remaining amount of solutions A and B was started, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 70 &lt; 0 &gt; C for 2 h.

The results are shown in Table 3.

Comparative Example 4g:

87 wt% Copolymer of HBVE-23EO and 13 wt% Na methacrylate

Polymerization at pH 7.5-8.0 (starting azo), Method (B)

A solution B (1.6 g of 2,2 ') of 66 g of water, a solution A (35.6 g of VME-23EO, 4.4 g of methacrylic acid and 18 g of water) and part (1.9 g) of Part A (2.9 g) (Wako VA-44) and 36 g of water) were initially charged in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen line and an addition line And filled in a glass reactor equipped. The initial charge was heated to 70 캜 under nitrogen and the addition of the remaining amount of solutions A and B was started, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 70 &lt; 0 &gt; C for 2 h.

The results are shown in Table 3.

Example 4h:

87 wt% Copolymer of VME-24EO and 13 wt% Na methacrylate

Polymerization at pH 7.5-8.0 (peroxide starting material)

A solution B (0.8 g (75% solution) of tert-butyl hydroperoxide in solution of 66 g of water, part (2.9 g) of solution A (35.6 g of VME-23EO, 4.4 g of acrylic acid and 18 g of water) -Butyl perpivalate and 36 g of isopropanol) were initially charged in a glass reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen line and addition line. The initial charge was heated to 75 占 폚 under nitrogen, and the addition of the remaining amounts of solutions A and B was started, where Solution A was added over 3 hours and Solution B was added over 4 hours. The reaction mixture was then stirred at 75 &lt; 0 &gt; C for 2 h. Isopropanol was distilled off.

The results are shown in Table 3.

Example 5:

Copolymerization of VME alkoxylate with HEMA and HPMA phosphate compared to HBVE alkoxylate

Example 5a:

A copolymer of 80 wt% VME-67EO and 20 wt% hydroxyethyl methacrylate phosphate

The experimental apparatus consisted of a 1000 ml jacket reactor, a temperature controller, a stirring motor with a propeller stirrer, a temperature sensor, a pH probe and an N ₂ inlet. 172.80 g of water and 103.38 g of VME-67 EO are added to the reactor. Subsequently, N ₂ is injected to replace oxygen. Set the temperature controller to T = 75 ° C and heat the reactor contents.

At about 60 占 폚, 25.94 g of hydroxyethyl methacrylate phosphate (HEMA-P) in 137.12 g of water are added. A pH of about 1.0 - 1.5 is reached. To this, 9.02 g of 50% NaOH is added to achieve a pH of about 3. When HEMA-P solution is added, the temperature drops to 50 캜. The reactor contents are then heated to 60 占 폚. Subsequently, 1.32 g of Wako VA-044 (2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in 13.2 g of water) is added. After a reaction time of 3 h, the reactor contents are cooled to 25 占 폚.

The slightly yellowish product of the yellow obtained has a pH of about 2.5 and a solids content of 30%. The average molar mass (Mw) of the polymer is 29 000 g / mol. The polydispersity is 1.25. The conversion is about 75% polymer (measured by GPC).

The results are shown in Table 4.

Example 5b:

84 wt% Copolymer of VME-135 EO and 16 wt% hydroxyethyl methacrylate phosphate

For example, the same apparatus as 5a was used.

172.80 g of water and 106.38 g of VME-135 EO are added to the reactor. Subsequently, N ₂ is injected to replace oxygen. Set the temperature controller to T = 75 ° C and heat the reactor contents. At about 60 [deg.] C, 19.79 g of hydroxyethyl methacrylate phosphate (HEMA-P) in 104.6 g of water are added. A pH of about 1.0 - 1.5 is reached. Thereafter, 7.05 g of 50% NaOH is added to this to achieve a pH of about 3. When HEMA-P solution is added, the temperature drops to 50 캜. The reactor contents are then heated to 60 占 폚. Then, 1.26 g of Wako VA-044 (2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in 11.3 g of water) is added.

After a reaction time of 3 h, the reactor contents are cooled to 25 占 폚.

The results are shown in Table 4.

Example 5c:

A copolymer of 89 wt% VME-135EO and 11 wt% hydroxyethyl methacrylate phosphate

For example, the same apparatus as 5a was used.

328.3 g of water and 202.12 g of VME-135 EO are added to the reactor. Subsequently, N ₂ is injected to replace oxygen. Set the temperature controller to T = 75 ° C and heat the reactor contents. At about 60 占 폚, 25.06 g of hydroxyethyl methacrylate phosphate (HEMA-P) in 132.5 g of water are added. A pH of about 1.0 - 1.5 is reached. Then, to this is added 8.90 g of 50% NaOH to achieve a pH of about 3. When HEMA-P solution is added, the temperature drops to 50 캜. The reactor contents are then heated to 60 占 폚. Then, 2.27 g of Wako VA-044 (2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in 21.6 g of water) is added.

After a reaction time of 3 h, the reactor contents are cooled to 25 占 폚.

The results are shown in Table 4.

Example 5d:

A copolymer of 92 wt% VME-135EO and 8 wt% hydroxyethyl methacrylate phosphate

For example, the same apparatus as 5a was used.

328.3 g of water and 202.12 g of VME-135 EO are added to the reactor. Subsequently, N ₂ is injected to replace oxygen. Set the temperature controller to T = 75 ° C and heat the reactor contents. At about 60 占 폚, 16.71 g of hydroxyethyl methacrylate phosphate (HEMA-P) in 88.31 g of water are added. A pH of about 1.0 - 1.5 is reached. Then, 5.78 g of 50% NaOH is added to this to achieve a pH of about 3. When HEMA-P solution is added, the temperature drops to 50 캜. The reactor contents are then heated to 60 占 폚. Then 2.19 g of Wako VA-044 (2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in 21.6 g of water) is added.

After a reaction time of 3 h, the reactor contents are cooled to 25 占 폚.

The results are shown in Table 4.

Example 5e:

84 wt% Copolymer of VME-10PO-125EO and 16 wt% hydroxyethyl methacrylate phosphate

For example, the same apparatus as 5a was used.

328.3 g of water and 202.12 g of VME-10PO-125 EO are added to the reactor. Subsequently, N ₂ is injected to replace oxygen. Set the temperature controller to T = 75 ° C and heat the reactor contents. At about 60 캜, 37.59 g of hydroxyethyl methacrylate phosphate (HEMA-P) in 198.7 g of water are added. A pH of about 1.0 - 1.5 is reached. Then, 13.45 g of 50% NaOH is added to this to achieve a pH of about 3. When HEMA-P solution is added, the temperature drops to 50 캜. The reactor contents are then heated to 60 占 폚. Then, 2.4 g of Wako VA-044 (2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in 21.6 g of water) is added.

After a reaction time of 3 h, the reactor contents are cooled to 25 占 폚.

The results are shown in Table 4.

Example 5f:

84 wt% Copolymer of VME-135 EO and 16 wt% hydroxypropyl methacrylate phosphate

For example, the same apparatus as 5a was used.

328.3 g of water and 202.12 g of VME-135 EO are added to the reactor. Subsequently, N ₂ is injected to replace oxygen. Set the temperature controller to T = 75 ° C and heat the reactor contents. At about 60 캜, 38.81 g of hydroxypropyl methacrylate phosphate (HPMA-P) in 198.7 g of water are added. A pH of about 1.0 - 1.5 is reached. Thereafter, 11.5 g of 50% NaOH is added to this to achieve a pH of about 3. When the HPMA-P solution is added, the temperature falls to 50 ° C. The reactor contents are then heated to 60 占 폚. Then, 2.4 g of Wako VA-044 (2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in 21.6 g of water) is added.

After a reaction time of 3 h, the reactor contents are cooled to 25 占 폚.

The results are shown in Table 4.

Example 5g:

A copolymer of 98 wt% VME-135EO and 2 wt% maleic anhydride

For example, the same apparatus as 5a was used.

218.88 g of water and 134.75 g of VME-135 EO are added to the reactor. Subsequently, N ₂ is injected to replace oxygen. Set the temperature controller to T = 75 ° C and heat the reactor contents. At about 60 [deg.] C, 2.67 g of maleic anhydride (MA) in 7.9 g of water are added. Thereafter, 2.68 g of 40% KOH is added to this to achieve a pH of about 3. When the MA solution is added, the temperature drops to 50 ° C. The reactor contents are then heated to 60 占 폚. Subsequently, 1.37 g of Wako VA-044 (2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in 12.37 g of water) is added.

After a reaction time of 3 h, the reactor contents are cooled to 25 占 폚.

The results are shown in Table 4.

Comparative Example 5a:

84 wt% Copolymer of HBVE-135 EO and 16 wt% hydroxyethyl methacrylate phosphate

For example, the same apparatus as 5a was used.

217.15 g of water and 133.68 g of HBVE-135 EO are added to the reactor. Subsequently, N ₂ is injected to replace oxygen. Set the temperature controller to T = 75 ° C and heat the reactor contents. At about 60 占 폚, 25.72 g of hydroxyethyl methacrylate phosphate (HEMA-P) in 135.95 g of water are added. Thereafter, 9.13 g of 50% NaOH is added to this to achieve a pH of about 6.5. When HEMA-P solution is added, the temperature drops to 50 캜. The reactor contents are then heated to 60 占 폚. Subsequently, 1.59 g of Wako VA-044 (2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in 11.34 g of water) is added.

After a reaction time of 3 h, the reactor contents are cooled to 25 占 폚.

The results are shown in Table 4.

Comparative Example 5b:

89% by weight Copolymer of HBVE-135EO and 11% by weight hydroxyethyl methacrylate phosphate

For example, the same apparatus as 5a was used.

217.15 g of water and 133.68 g of HBVE-135 EO are added to the reactor. Subsequently, N ₂ is injected to replace oxygen. Set the temperature controller to T = 75 ° C and heat the reactor contents. At about 60 &lt; 0 &gt; C, 17.15 g of hydroxyethyl methacrylate in 90.64 g of water

Phosphate (HEMA-P) is added. Thereafter, 9.5 g of 50% NaOH is added to this to achieve a pH of about 6.5. When HEMA-P solution is added, the temperature drops to 50 캜. The reactor contents are then heated to 60 占 폚. Subsequently, 1.51 g of Wako VA-044 (2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in 11.34 g of water) is added.

After a reaction time of 3 h, the reactor contents are cooled to 25 占 폚.

The results are shown in Table 4.

Comparative Example 5c:

98% by weight Copolymer of HBVE-135EO and 2% by weight maleic anhydride

For example, the same apparatus as 5a was used.

434.3 g of water and 267.37 g of HBVE-135 EO are added to the reactor. Subsequently, N ₂ is injected to replace oxygen. Set the temperature controller to T = 75 ° C and heat the reactor contents. At about 60 [deg.] C, 5.48 g of maleic anhydride (MA) in 28.62 g of water are added. Then 5.3 g of 40% KOH is added to this to achieve a pH of about 6.5. When the MA solution is added, the temperature drops to 50 ° C. The reactor contents are then heated to 60 占 폚. Then, 2.73 g of Wako VA-044 (2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in 24.55 g of water) is added.

After a reaction time of 3 h, the reactor contents are cooled to 25 占 폚.

The results are shown in Table 4.

Application test

Test Methods:

Diffusion test using a polycarboxylate ether plasticizer based on VME ethoxylate as compared to HBVE ethoxylate.

According to DIN EN 196-1, a mortar composed of 450 g of Heidelberg cement CEM I, 42.5 R, 1350 g of standard sand and 225 g of water (less than water added with a plasticizer) was prepared. After 90 seconds during the mortar preparation, a plasticizer (0.1 to 0.3% by weight based on the cement) was added, together with the defoamer triisobutyl phosphate (7% by weight based on the dry weight of the plasticizer). After the addition, mixing was continued for 60 s. Then, the mortar was charged into a conical mold disposed at the center on the oscillation table at the origin of the orthogonal coordinate system having two axes (unit of cm). Excess mortar was wiped from the top edge and the mold was lifted so that the conical mortar cake remained on the diffusion table. After 15 strokes (upward strokes) by a rocking table, the diameter of the cake along the axis was measured. The larger the diameter of the mortar cake, the better the flow characteristics of the mortar. The measurements were repeated after 30, 60 and 90 minutes with the same mortar sample. The temperature was 23 +/- 1 占 폚.

The polymers used in each case, their amounts and test results are shown in Table 5. &lt; tb &gt;&lt; TABLE &gt;

Feedback on performance experiments

The examples in the table show that the experiment using VME ethoxylate has a better effect on mortar plasticization compared to the HBVE-based experiment.

In the blank test, the diameter of the mortar cake after 1 min was 17.65 cm. The addition of 0.12% HBVE-based plasticizer (Comparative Example V2) leads to a mortar cake diameter of 19.55 cm after 1 min. The corresponding VME-based product (Example 2) reaches 21.15 cm. The VME-based product is also better when the concentration is doubled; With the VME-based product reaching 26 cm (Experiment 4) and reaching only 21.1 cm with the HBVE-based product.

The experiment also shows that a better performance result is achieved with the polymer prepared according to process (B), compared to the polymer prepared according to process (A): in the amount of 0.12% by weight, the process The best experiments with the VME-based products thus prepared provided 21.15 cm. In Experiments 7 and 9, about 28 to 29 cm was achieved by the VME-based product prepared according to process (B), although the amount of polymer was less than 0.1 wt% as in Experiment 2 (0.12 wt%).

While not wishing to refer to the theory, it is believed that this effect is due to the fact that compound (I) self-polymerizes relatively easily due to their relatively high reactivity. Since compound (I) is initially charged in process (A) and comonomer is added slowly, the formation of the block structure is promoted. It is believed that process (B), in which both monomers are added slowly, results in a more uniform incorporation of the VME monomer into the copolymer. As a result, a considerably good effect as a concrete plasticizer can be clearly achieved.

Claims (39)

The unsaturated compounds of formula (I)

(Wherein,
R ¹ , R ² and R ³ are the same or different and each independently H, CH ₃ ,
R ⁴ is a linear or branched C ₁ -C ₃₀ - alkylene,
R ⁵ and R ⁶ are the same or different and are each independently selected from H, C ₁ -C ₂₀ -alkyl, C ₃ -C ₁₅ -cycloalkyl, aryl, -CH ₂ -OC ₁ -C ₂₀ -alkyl, CH ₂ -OC ₂ -C ₂₀ -alkenyl, R ⁵ and R ⁶ together may form C ₃ -C ₆ -alkylene,
R ⁷ are the same or different and, independently, H, C ₁ -C ₄ - alkyl,

Lt;
R ⁸ is C ₁ -C ₂₂ -alkyl, C ₂ -C ₂₂ -alkenyl,
and n is an integer of 2 to 200). The method of claim 1, wherein, R ⁴ is C ₂ -C ₄ - alkylene group, R ^5, and R ⁶ are the same or different, each independently represents _{H, -CH 3, -CH 2 -CH} 3, -C 3 - C ₁₁ - alkyl, C ₁₂ -C ₂₂ - alkyl, phenyl, -CH ₂ -OC ₁ -C ₁₀ - alkyl, CH ₂ -OC ₂ -C ₁₀ - is a group selected from alkenyl, R ⁷ is H or C ₁ -C ₄ -alkyl, and n is 5 to 140. The method of claim 1, wherein the compound is an unsaturated compound (Ia)

(Wherein,
R &lt; ³ &gt; is H or methyl,
R ⁴ is a linear or branched C ₂ -C ₁₀ -alkylene group,
R ⁵ and R ⁶ are each independently H, methyl or ethyl with the proviso that the sum of the carbon atoms in the R ⁵ and R ⁶ residues per alkoxy group is in each case 0 to 2,
and n is from 5 to 160). The unsaturated compound according to claim 1, wherein the compound is an unsaturated compound (Ib):

(Wherein n is 20 to 140). The unsaturated compound according to claim 4, wherein n is 20 to 30. A mixture comprising a compound of formula (I) according to claim 1. A polymer comprising the compound of formula (I) according to claim 1 as a monomer. A polymer comprising the compound of formula (Ia) according to claim 3 as a monomer. A polymer comprising the compound of formula (Ib) according to claim 4 as a monomer. 10. The polymer according to any one of claims 7 to 9, wherein at least one further monomer different from the compound of formula (I), (Ia) or (Ib) is present in the polymer. 11. The polymer of claim 10, wherein the further monomer is at least one monoethylenically unsaturated monomer. 12. The polymer according to claim 11, wherein the monoethylenically unsaturated monomer is a monomer containing an acid group, and the acid group can also be completely or partially neutralized. The polymer according to claim 12, wherein the acid group is a group selected from the group of a carboxylic acid group, a sulfonic acid group, a phosphoric acid group or a phosphonic acid group. 14. The composition according to claim 13, wherein the polymer is selected from the group consisting of acrylic acid, methacrylic acid, (meth) acrylic acid anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, mesaconic acid, citraconic acid or methylenemalonic acid, A polymer comprising at least one monomer having a carboxylic acid group selected. 14. The composition of claim 13, wherein the polymer is selected from the group consisting of vinylphosphonic acid, hydroxyethyl with (poly) phosphoric acid, ester of hydroxypropyl or hydroxybutyl (meth) acrylate, monovinyl phosphate, allylphosphonic acid, monoallyl phosphate, 3 Mono (2-hydroxy-3-vinyloxypropyl) phosphate, mono (1-phosphonooxymethyl-2- (3-allyloxy-2-hydroxypropyl) phosphate, mono [2- (allyloxy-1-phosphonoxymethylethyl)] phosphate, 2-hydroxy-4-vinyloxymethyl At least one monomer having a phosphoric acid group or a phosphonic acid group selected from the group of -1,3,2-dioxaphosphol, 2-hydroxy-4-allyloxymethyl-1,3,2-dioxaphosphol, &Lt; / RTI &gt; 14. The composition of claim 13, wherein the polymer is selected from the group consisting of vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2- acrylamodimethyldodecylsulfonic acid, 2- (meth) acryloxyethanesulfonic acid, 3- (meth) At least one monomer having a sulfonic acid group selected from the group of sulfonic acid, methanesulfonic acid, propanesulfonic acid, allyloxybenzenesulfonic acid, vinylbenzenesulfonic acid, vinyltoluenesulfonic acid, allylsulfonic acid, methallylsulfonic acid or salts thereof. 10. The composition of any one of claims 7 to 9, wherein the at least one monoethylenically unsaturated monomer present is selected from the group consisting of styrene, butadiene, methyl methacrylate, (meth) acrylate, ethyl acrylate, dibutyl maleate, methyl alpha (Meth) acrylic acid, maleic acid (anhydride), itaconic acid, vinylphosphonic acid, N-vinylpyrrolidone, N, N-dimethyl-N, N-diallylammonium chloride (Meth) allyl alkoxylate or hydroxybutyl vinyl ether (meth) acrylate, vinyl imidazole, vinyl alcohol, vinyl acetate, allylsulfonic acid, 2-acrylamido- Alkoxylate. 18. The composition of claim 17 wherein the at least one monoethylenically unsaturated monomer present is selected from the group consisting of acrylic acid, methacrylic acid, (meth) acrylate, maleic acid (anhydride), (iso) prenyl alkoxylate, (meth) &Lt; / RTI &gt; is a hydroxybutyl vinyl ether alkoxylate. 19. The composition of claim 18, wherein the unsaturated compound of formula (I) is selected from the group consisting of acrylic acid, methacrylic acid, (meth) acrylate, maleic acid (anhydride), (iso) prenyl alkoxylate, (meth) In addition to the vinyl ether alkoxylate, no other monomer is present. The polymer of claim 17, wherein no other monomer is present in addition to the unsaturated compound of formula (I) and acrylic acid and methacrylic acid or acrylic acid and maleic acid (anhydride) or methacrylic acid and maleic acid (anhydride). The polymer according to claim 20, wherein, in addition to the unsaturated compounds of formula (I), acrylic acid, methacrylic acid and maleic acid (anhydride), no other monomer is present. 22. The polymer according to any one of claims 7 to 21, wherein from 5 to 99.9% by weight, based on the total amount of monomers, of an unsaturated compound of formula (I), (Ia) or (Ib) is present in the polymer. 22. A composition according to any one of claims 7 to 21, wherein, in each case, from 5 to 99.9% by weight, based on the total amount of monomers, of an unsaturated compound of formula (I) and from 95 to 0.1% by weight of another monoethylenically unsaturated monomer Existing polymer. The composition according to claim 18, wherein, in each case in relation to the total amount of monomers, from 5 to 99.9% by weight of the unsaturated compound of formula (I) and from 95 to 0.1% by weight of the total of acrylic acid, methacrylic acid, (meth) (Anhydride), (iso) prenyl alkoxylate, (meth) allyl alkoxylate or hydroxybutyl vinyl ether alkoxylate. 25. The polymer according to any one of claims 7 to 24, wherein the number average molecular weight M _n of the polymer is from 1000 g / mol to 1 000 000 g / mol. To claim 7 according to any one of claim 24, wherein the number average molecular weight M _n of the polymer is 5000 g / mol to 100 000 g / mol of the polymer. 26. A process for the preparation of a polymer according to any one of claims 7 to 26, wherein the unsaturated compound (I) and optionally one or more further monomers are subjected to free radical polymerization. 28. The process according to claim 27, wherein said process is a copolymerization of free radical polymerization of an unsaturated compound (I) and at least one further monoethylenically unsaturated monomer. 29. The method of claim 28, wherein the monoethylenically unsaturated monomer is a monomer comprising an acid group, and wherein the acid group can also be completely or partially neutralized. The method according to claim 29, wherein the acid group is a group selected from the group of carboxylic acid group, sulfonic acid group, phosphoric acid group or phosphonic acid group. 30. The method according to any one of claims 27 to 29, wherein the unsaturated compound (Ia) is included. 30. The method according to any one of claims 27 to 29, wherein the unsaturated compound (Ib) is included. 33. The process according to any one of claims 27 to 32, wherein the free radical polymerization is carried out in an aqueous solution. 34. The method of claim 33, wherein the pH during the polymerization is between 1 and 6. 34. The method of claim 33, wherein the pH during the polymerization is from 1 to 3. A process as claimed in any one of claims 28 to 35 wherein the free radical polymerization is carried out at an early stage in the reactor by introducing some of the unsaturated compounds (I), (Ia) or (Ib), some of the other monomers and also some polymerization initiator (I), (Ia) or (Ib), another monomer and also a polymerization initiator in a polymerization reactor. 37. The method of claim 36, wherein the amount of the initially charged monomers does not exceed 25% by weight of the total amount of monomers. Cement additives, crushing aids in the manufacture of cements, concrete plasticizers, additives for hydraulic binders, reactive plasticizers for the production of plastics, rubber or latex, associative thickeners and antioxidants, or for the production of polyether siloxanes, 26. Use of a polymer according to any one of claims &lt; RTI ID = 0.0 &gt; 26 &lt; / RTI &gt; 26. A mixture comprising a polymer according to any one of claims 7 to 26.